EP2051972A1

EP2051972A1 - Process for one-stage preparation of 2-methyltetrahydrofuran from furfural over two catalysts in a structured bed

Info

Publication number: EP2051972A1
Application number: EP08761344A
Authority: EP
Inventors: Tobias Wabnitz; Daniel Breuninger; Jens Heimann; Rene Backes; Rolf Pinkos
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-07-02
Filing date: 2008-06-24
Publication date: 2009-04-29
Anticipated expiration: 2028-06-24
Also published as: EP2051972B1; TWI417288B; CN101558052B; TW200918514A; WO2009003881A1; CN101558052A; JP5484321B2; KR20100028521A; ATE478060T1; US20100048922A1; DE502008001144D1; JP2010531838A; KR101515644B1; US8168807B2

Abstract

The present invention provides a process for preparing 2-methyltetrahydrofuran by one-stage hydrogenation of furfural with a hydrogen-comprising gas in the presence of a structured bed of at least one copper catalyst and at least one catalyst which comprises at least one noble metal from groups 8, 9 and/or 10 of the periodic table of the elements applied on a support material.

Description

Process for the single-stage production of 2-methyltetrahydrofuran from furfural on two catalysts in structured bed

description

The present invention relates to a process for the one-stage preparation of 2-methyltetrahydrofuran from furfural on at least two catalysts in structured bed.

2-Methyltetrahydrofuran (hereinafter 2-Me-THF) is an organic solvent with high solubility. 2-Me-THF is used as a replacement solvent for chemical syntheses of tetrahydrofuran (hereinafter THF), from which it advantageously differs by its lower, with increasing temperature decreasing water solubility, as a fuel additive, as it better with common fuels based on hydrocarbon is miscible as alcoholic additives, and used as a comonomer for the preparation of polyethers having improved properties over homopolymers.

2-Me-THF is available from renewable raw materials. 2-Me-THF can be obtained from plant waste by digesting the hemicelluloses it contains into furfural and converting it into 2-Me-THF, thus contributing to sustainable development.

While the production of furfural from plant, in particular agricultural wastes is known and has reached a high level of elaboration, the conversion of furfural to 2-Me-THF is technically not yet satisfactorily resolved.

The elemental reactions of the hydrogenating reaction of furfural are known and have been described in detail by Zheng et al., Journal of Molecular Catalysis A: Chemical (2006), 246 (1-2), 18-23. The authors consider 2-methylfuran to be a precursor in the preparation of 2-Me-THF and describe major and minor hydrogenation reactions, including the formation of carbon monoxide by decarboxylation.

Although 2-Me-THF is often produced in small amounts in the hydrogenating reactions of furfural, there are only a few papers describing the direct conversion of furfural to 2-Me-THF.

Kyosuke et al., J. Pharm. Soc. Jpn 66 (1946), 58 show that the direct conversion of furfural to 2-methyl-THF on Raney nickel catalysts at 260 ⁰ C provides only small amounts of the desired product. Kyosuke et al. instead, a two-step process via methylfuran as an isolated intermediate and the use of different catalysts for the two stages. Thus, in the first stage, Cu-chromite is used after Adkins and in the second stage Raney-nickel.

Proskuryakov et al., Trudy Leningradskogo Tekhnologicheskogo Instituta imeni Lensoveta (1958), 44, 3-5, described a maximum yield of 42% 2-Me-THF in the conversion of furfural to a 1: 1 mixture from a Raney Nickel and a Kupferhrromitkatalysator in an autoclave at 220 ⁰ C and 160 atm. The authors show that higher 2-Me-TH F fractions can not be obtained in this way due to side reactions to glycols and other unspecified furfural ring-opening products.

A further disadvantage was the difficulty of isolating and purifying 2-Me-THF from the reaction mixture mixtures obtained, since the by-products THF, 2-pentanone and water as pure substances or in the form of their azeotropes have boiling points similar to those of 2-Me-THF. Thus, the boiling points of the azeotropic water / 2-Me-THF at 73 ° C, water / THF at 64 ° C and water / 2-pentanone at 84 ° C while the pure substances THF at 66 ° C, 2-Me-THF at 80 ⁰ C and 2-pentanone at 102 ⁰ C boiling.

From US-A 6,479,677 a two-step process for the preparation of 2-Me-THF using each a separate catalyst for each stage is known. Each stage is carried out in a separate reactor with differing catalysts. This gas-phase process involves the hydrogenation of furfural on a Cu-chromite catalyst to methylfuran, which is then reacted on a nickel catalyst to 2-Me-THF.

However, the disclosed process has a number of disadvantages. Thus, different reaction conditions are required for the individual stages of the reaction, which makes the technical design difficult and requires a spatial separation of the individual reactors. The addition of hydrogen is required separately for each hydrogenation step and a large excess of hydrogen, as often desired in gas phase reactions, is not tolerated. In addition, the formation of carbon monoxide, which always occurs in small amounts from thermal furfural furfural, leads to deactivation of the nickel catalyst and formation of highly toxic, volatile Ni (CO) ₄ by the accumulation of critical impurities such as carbon monoxide the economically desirable Kreisgasfahrweise impossible.

It is an object of the present invention to provide a process for the one-step preparation of 2-methyltetrahydrofuran from furfural using specific catalysts without isolation or purification of intermediates, with the aid of which 2-methyltetrahydrofuran is particularly useful. can be obtained by reaction in a reactor and in circulation mode in good yield and purity.

Accordingly, the present invention relates to a process for the one-stage hydrogenation of furfural with a hydrogen-containing gas in the presence of a structured bed of at least one copper catalyst and at least one catalyst having at least one noble metal from groups 8, 9 and / or 10 of the Periodic Table of the Elements applied a carrier material. In a preferred embodiment, the present invention relates to a process for the one-stage hydrogenation of furfural with a hydrogen-containing gas in the presence of two catalysts, wherein the first one copper catalyst and the second catalyst as active metal at least one noble metal from groups 8, 9,10 of the Periodic Table Elements, in particular ruthenium, rhodium, iridium gold, palladium and / or platinum, preferably palladium and / or platinum, applied to a carrier material, in structured bed.

In this application, single-stage or one-stage hydrogenation is understood to mean a process which, starting from furfural, leads to the end product 2-Me-THF without isolation or purification of intermediates.

As the first catalyst of the preferred embodiment, the catalyst is referred to, with which the stream of starting materials, the furfural and the hydrogen-containing gas, first comes in contact with the reactor, while the second catalyst is arranged in the flow direction spatially after the first catalyst and therefore is flowed through only after this time.

First catalyst

The first catalyst is a copper catalyst which preferably contains, in addition to copper as additional active metals, one or more elements of groups 2, 6 and / or 12 of the Periodic Table of the Elements (New IUPAC Nomenclature), in particular chromium, manganese, zinc, barium. The total content of the aforementioned active metals is 10-100 wt .-%, preferably 15-80 wt .-%, calculated as oxide. The copper content of the catalyst is at least 10% by weight, calculated as oxide, but preferably at least 15% by weight, particularly preferably 15 to 80% by weight.

Suitable first catalysts are full catalysts in which the catalytically active metals are present without support materials, corresponding to an active metal content of 100% by weight, and precipitation catalysts or supported catalysts.

A preferred unsupported catalyst is the catalyst of the composition 24-26% by weight of copper oxide, 1% by weight of chromium (VI) oxide, 1% by weight of chromium (III) oxide, 0-4% by weight of graphene. phit, 65-67 wt .-% copper chromite, which is sold as catalyst E 403-TU by Engelhard, Iselin USA.

Precipitation catalysts can be prepared by reacting their catalytically active components from their salt solutions, in particular from the solutions of their nitrates and / or acetates, for example by adding solutions of alkali metal and / or alkaline earth metal and / or carbonate solutions, for example as sparingly soluble Hydroxides, oxyd hydrates, basic salts or carbonates precipitates, the resulting precipitates then dried and then converted by calcination at generally 300 to 700 ⁰ C, in particular 400 to 600 ⁰ C, in the corresponding oxides, mixed oxides and / or mixed-valent oxides, the by treatment with hydrogen or hydrogen-containing gases at usually 50 to 700 ^° C, in particular 100 to 400 ^° C, reduced to the respective metals and / or oxidic compounds lower oxidation state and converted into the actual, catalytically active form become. This is usually reduced until no more water is formed. In the preparation of precipitation catalysts containing a support material, the precipitation of the catalytically active components can be carried out in the presence of the relevant support material. The catalytically active components can advantageously but also be precipitated simultaneously with the carrier material from the relevant salt solutions. In the process according to the invention, preference is given to using hydrogenation catalysts which contain the hydrogenation-catalyzing metals or metal compounds deposited on a support material.

In addition to the abovementioned precipitation catalysts, which additionally contain a support material in addition to the catalytically active components, supported catalysts for which the catalyst-hydrating components, e.g. by impregnation, have been applied to a substrate.

The nature of the application of the catalytically active metals to the support is usually not critical and can be accomplished in various ways. The catalytically active metals can be applied to these support materials, for example by impregnation with solutions or suspensions of the salts or oxides of the elements concerned, drying and subsequent reduction of the metal compounds to the respective metals or compounds of lower oxidation state by means of a reducing agent, preferably with hydrogen or complex hydrides , Another possibility for applying the catalytically active metals to these carriers is to impregnate the carrier with solutions of thermally easily decomposable salts, for example with nitrates, or thermally easily decomposable complex compounds, for example carbonyl or hydrido complexes of the catalytically active metals, and the so impregnated carrier for the purpose of thermal decomposition of the adsorbed metal compounds to temperatures of 300 to 600 ⁰ C to heat. This thermal decomposition is preferably carried out under a protective gas atmosphere. Suitable shielding gases are, for example, nitrogen, carbon dioxide, hydrogen or the noble gases. Furthermore, the catalytically active metals can be deposited on the catalyst support by vapor deposition or by flame spraying. The content of these supported catalysts on the catalytically active metals is in principle not critical for the success of the process according to the invention. However, higher levels of catalytically active metals usually result in higher space-time conversions than lower levels.

In general, supported catalysts are used whose content of catalytically active metals, calculated as oxide, 10 to 90 wt .-%, preferably 15 to 80% by weight, based on the total catalyst is. Since these content data refer to the entire catalyst including carrier material, but the different carrier materials have very different specific weights and specific surface areas, these details can also be undershot or exceeded without adversely affecting the result of the process according to the invention , Of course, several of the catalytically active metals can be applied from the respective carrier material.

Both the activation of the precipitation catalysts and the supported catalysts can also be carried out in situ at the beginning of the reaction by the hydrogen present, but these catalysts are preferably activated separately prior to their use.

As support materials, in general, the oxides of aluminum, zirconia, silica, magnesium and calcium oxide can be used. Of course, mixtures of different carrier materials may also serve as carriers for heterogeneous catalysts which can be used in the process according to the invention. The following may be mentioned by way of example for the first catalyst which can be used in the process according to the invention: 25% by weight of copper oxide, 1% by weight of Cr ₂ O ₃ and 74% by weight of SiO ₂

Second catalyst

The second catalyst used according to the invention comprises as active metal at least one noble metal from groups 8, 9, 10 of the Periodic Table of the Elements, in particular ruthenium, rhodium, iridium gold, palladium and / or platinum, preferably palladium and / or platinum, particularly preferably palladium , on a carrier. The second catalyst may additionally comprise metals of groups 1, 2, 4 and 7 to 12 of the Periodic Table of the Elements. In particular, sodium, potassium, calcium or magnesium can be used as elements of groups 1 and 2 of the Periodic Table of the Elements. It preferably has no further active metals except palladium and platinum. The application of the active metals can be achieved by impregnating the support in aqueous metal salt solutions, such as, for example, aqueous palladium salt solutions, by spraying appropriate metal salt solutions onto the support or by other suitable methods. Suitable metal salts of platinum and palladium are the nitrates, nitrosyl nitrates, halides, carbonates, carboxylates, acetylacetonates, chlorides, chiorocomplexes or amine complexes of the corresponding metals, the nitrates being preferred.

In the case of catalysts comprising palladium and platinum and optionally also further active metals on the carrier, the metal salts or metal salt solutions can be applied simultaneously or in succession.

The coated or impregnated with the metal salt solution carriers are then, preferably at temperatures between 100 ⁰ C and 150 ⁰ C, dried and optionally calcined at temperatures between 200 ⁰ C and 600 ⁰ C, preferably between 350 ⁰ C and 450 ⁰ C. In the case of separate impregnation, the catalyst is dried after each impregnation step and optionally calcined as described above. The order in which the active components are soaked is freely selectable.

Subsequently, the coated and dried and optionally calcined supports are activated by treatment in a gas stream containing free hydrogen at temperatures between about 30 ° C and about 600 ° C, preferably between about 150 ° C and about 450 ° C. Preferably, the gas stream consists of 50 to 100 vol .-% H ₂ and 0 to 50 vol .-% N ₂ .

The metal salt solution or solutions are applied to the support (s) in an amount such that the total active metal content, based in each case on the total weight of the catalyst, is about 0.1 to about 30% by weight, preferably about 0.1 to about 10 wt%, more preferably about 0.25 to about 5 wt%, and especially about 0.5 to about 2.5 wt%.

Activated carbon, for example in the form of the commercial product supersorbon coal from Danube Carbon GmbH, 60388 Frankfurt, alumina, silica, silicon carbide, calcium oxide, titanium dioxide and / or zirconium dioxide or mixtures thereof, with activated carbon being preferably used ,

The procedure

The inventive method is characterized by a structured bed of the first and second catalyst. The one-stage hydrogenation according to the invention can be carried out in one or more, in particular two, three, four, five, six, seven, eight reactors. When using a plurality of reactors, the first catalyst may be in a first reactor or in a first group of at least two reactors and the bed of the second catalyst is in the second reactor or in the second group of at least two reactors. However, the single-stage hydrogenation is preferably carried out in a reactor.

The reaction mixture flows through the reactor or the reactors preferably from top to bottom. In this case, when using a reactor and correspondingly when using several reactors for the 20 to 80% of the total height of the catalyst bed, preferably the upper 40 to 60%, the total height of the bed after the reactor head of the single and the first reactor, the first catalyst (Copper catalyst) used. The remaining bed height is then formed by the second catalyst (palladium and / or platinum catalyst). If the reactor or reactors are flowed through from bottom to top, the catalysts are arranged in the reverse order.

When using a single reactor, it may be advantageous to separate the portion of the bed formed from the first catalyst from the portion formed from the second catalyst by introducing an intermediate layer of inert material. As an inert intermediate layer, for example, glass rings or metal rings are suitable. The hydrogenation of furfural to 2-Me-THF can therefore advantageously be carried out in one stage in a reactor.

In the context of the process according to the invention, the hydrogenation can be carried out in the gas phase or the liquid phase; preference is given to working in the gas phase. In general, the process is carried out in the gas phase at a temperature of about 150 to 250 ⁰ C, preferably about 190 to 230 ⁰ C. The pressures used are usually at 1 to 10 bar absolute, preferably about 1 to 3 bar abs. The pressure in this application is given as total pressure or absolute (abs.) Pressure.

In the liquid phase, the inventive method is generally at 150 to 250 ° C at pressures of 1 to 250 bar abs., Preferably at 20 to 200 bar abs., Performed.

In addition to the copper catalyst and the noble metal catalyst, which are required for carrying out the method according to the invention and referred to as the first and second catalyst, further catalysts may be in the reactor or in the reactors. For example, these catalysts can be used to improve product quality by removing impurities or by reacting by-products. For example, sulfur-containing components found in furfural in are usually present in a small amount, be removed by treatment with desulfurization catalysts or adsorbents based on copper and / or molybdenum and / or zinc oxides. As a by-product of handling furfural, small amounts of carbon monoxide are always produced. This by-product can be converted to methanol, for example, by hydrogenation over copper and / or ruthenium catalysts and thus removed, and ketone-type and aldehydic by-products can be converted into alcohols in an analogous manner. Catalysts which fulfill these and similar functions may, in addition to the catalysts which are absolutely necessary for carrying out the process according to the invention, be located at any point in the reactor. They can be incorporated both before the copper catalyst and after the noble metal catalyst and between the two catalysts. It is also conceivable to use such catalysts in a homogeneous mixture, as long as the structured bed of the copper catalyst and the noble metal catalyst is not canceled.

The process according to the invention can be carried out either continuously or batchwise, the continuous process being preferred. In the continuous process regime, the amount of hydrogenation furfur used is about 0.05 to about 3 kg per liter of catalyst per hour, more preferably about 0.1 to about 1 kg per liter of catalyst per hour.

Hydrogenating gases may be any of the gases that contain free hydrogen and that do not contain harmful amounts of catalyst poisons, such as CO. For example, reformer exhaust gases can be used. Preferably, pure hydrogen is used as the hydrogenation gas. However, it is also possible to additionally use inert carrier gases such as water vapor or nitrogen.

Wassstoff / furfural molar ratio

The mixing ratio of hydrogen and furfural is not critical as long as sufficient amounts of hydrogen (4 equivalents) are available for the conversion of furfural to 2-methyl-THF. A hydrogen excess is possible. In the continuous process, the hydrogen / furfural ratio at the reactor inlet is 4: 1 to 500: 1, preferably 5: 1 to 250: 1, more preferably 10: 1 to 100: 1.

In the liquid phase, the hydrogenation according to the invention can be carried out in the absence or presence of a solvent or diluent, i. it is not necessary to carry out the hydrogenation in solution.

However, a solvent or diluent may be used. The solvent or diluent used may be any suitable solvent or diluent. be set. The choice is not critical, as long as the solvent or diluent used is able to form a homogeneous solution with the furfural to be hydrogenated.

Examples of suitable solvents or diluents include the following: straight chain or cyclic ethers, such as tetrahydrofuran or dioxane, and aliphatic alcohols in which the alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 6 carbon atoms.

The amount of solvent or diluent used is not particularly limited and can be freely selected as needed, but those amounts are preferred which lead to a 10 to 70 wt .-% solution of the furfural intended for hydrogenation.

Furthermore, the hydrogenation reactor in the implementation of the hydrogenation in the

Liquid phase in a straight pass, that is, without product return, or in circulation (circuit), that is, a part of the reactor leaving the hydrogenation mixture is recycled, operated.

When carrying out the hydrogenation in the gas phase according to the invention, the reaction products are completely condensed and separated after leaving the reactor. The gaseous components, hydrogen and any additional carrier gas used, will partly recirculate back into the reactor (cycle gas mode). In the preferred cycle gas method, the ratio of circulating gas to fresh gas volumes is at least 1: 1, preferably at least 5: 1, more preferably at least 10: 1.

Suitable reactors are fixed-bed reactors, such as, for example, tube-bundle reactors. The choice of reactor type is not critical per se as long as the catalyst arrangement in the bed, that is, the order in which the reaction mixture flows through the catalysts is not changed. In the liquid mode, fluidized bed reactors are useful when the beds of the two types of catalysts are arranged to preclude mixing of the first and second catalysts in the operation of the reactor.

The reaction effluents of the hydrogenation according to the invention are condensed in a conventional manner, but preferably by cooling in a heat exchanger to 0 to 80 ⁰ C. After condensation, a phase separation occurs. The lower phase consists of more than 90% of water, while the upper phase, in addition to the desired product 2-Me-THF, has only small amounts of by-products which can be readily separated by optionally subsequent purifying distillation. 2-methyl-tetrahydrofuran (2-Me-THF) is by the inventive method in very good Yield and purity. The phase separation can be carried out at ambient temperature. However, the reaction effluents are preferably condensed at 60 ⁰ C, since at this temperature, the miscibility of 2-methyl-THF and water is particularly low.

In the following, the method of the invention will now be explained in more detail with reference to some embodiments.

Examples

Preparation Example Catalyst

4 kg of supersorbone coal (4 mm strands, manufacturer Danube Carbon GmbH) were placed in an impregnating drum and with 2.8 kg of a based on palladium 7.2 wt .-% aqueous solution of palladium (II) nitrate at room temperature with Help of a fine nozzle (1 mm) sprayed. The liquid was completely in the pores of the

Coal carrier added. The material was then dried for 40 hours at 100 ⁰ C in a warming cabinet.

Subsequently, the dried catalyst was activated (reduced) at 200 ^° C. in a stream of water. The catalyst thus prepared contained 5% by weight of palladium, based on the weight of the catalyst.

Analysis of the hydrogenation products

The reaction products 2-Me-THF, 2-pentanone, 3-pentanone, 1-pentanol, THF, furan and methylfuran and the starting material furfural were analyzed by gas chromatography. The mixtures were diluted with methanol or acetone (dilution 1:10 to 1: 100) or undiluted in the GC chromatograph (company HP, carrier gas: hydrogen) on a 30 m DB1 column (J + W) sprayed and at Oven temperatures of 60 ⁰ C to 300 ° C (heating rate 8 Kelvin per minute to 220 ⁰ C, then 20 Kelvin per minute to 300 ⁰ C) with a flame ionization detector (temperature: 290 ⁰ C) analyzed. The purity was determined by integration of the signals of the chromatogram.

Example 1 In a continuous hydrogenation plant consisting of an evaporator, an oil-heated 3.81 jacketed tubular reactor and a separator and a cycle gas compressor, furfural was continuously hydrogenated on fixed bed catalysts in the gas phase.

The tubular reactor was charged with 450 g of a Pd catalyst (5% Pd / Supersorbon coal, 4 mm strands), then above with 530 g of the copper chromite catalyst E 403-TU from Engelhard Iselin; USA now BASF (24-26 wt% copper oxide, 1 wt% Chromium (VI) oxide, 1% by weight chromium (III) oxide, 0-4% by weight graphite, 65-67% by weight copper chromite, tablets 3 mm × 3 mm).

The tube reactor was flowed through from top to bottom. The catalysts were activated by a method known to the expert without pressure with nitrogen / hydrogen mixtures at 200 ⁰ C, so that the content of hydrogen in the mixed gas was slowly increased from 0 to 100%. Subsequently, the system was pressed with hydrogen to 4 bar, fresh gas hydrogen adjusted to 450 NL / h, the evaporator to 230 ⁰ C, the temperature of the reactor to 220 ⁰ C and the recycle gas put into operation. In the evaporator 400 g / h single-stage furfural were promoted. During the hydrogenation, the recycle gas was adjusted to 240 g / h, 83 NL / h of exhaust gas was sent for combustion. Under these conditions, over 440 h furfural> 99% was implemented, the selectivity to 2-MeTHF was> 80%. The upper phase of the two-phase discharge had the following composition: furan, 2-methylfuran, THF <0.5% by weight, 2-MeTHF 84% by weight, 2-pentanone 2.4% by weight, 2-pentanol 1, 3% by weight, 1-pentanol 4 wt .-%, methyl-gamma-butyrolactone 5 wt .-%, balance to 100% unidentified by-products. The by-products could be removed by prior art distillation to give the desired product 2-MeTHF in> 99% purity.

Example 2

In an electrically heatable, vertically installed quartz tube as a reactor (inner diameter 2.5 cm, length 60 cm), 50 mL (21 g) of a palladium-carbon catalyst according to Example 1 (5% Pd on Supersorbon K, 4 mm strands) with 10 mL quartz glass rings (to separate the catalyst layers) and 50 mL (30 g) of a copper-chromite catalyst E 403-TU from Engelhard Iselin; USA (24-26% by weight of copper oxide, 1% by weight of chromium (VI) oxide, 1% by weight of chromium (III) oxide, 0-4% by weight of graphite, 65 to 67% by weight of copper chromite , Tablets 3 mm x 3 mm) and covered with a further 100 ml of quartz glass rings (as evaporating section).

The quartz tube with this structured catalyst / quartz glass ring bed was provided with a gas and a liquid feed tube and installed so that the reaction products were condensed and collected in a glass spiral cooler. The reactor was flowed through from top to bottom, that is, the reaction mixture flowed through first the copper chromite catalyst, then the Pd catalyst.

The catalysts were activated by treatment with hydrogen, first diluted in a stream of nitrogen, later in pure form, each at ambient pressure and 200 ° C for 2 h. Then, 5 mL / hr (about 5.8 g / hr) furfural was then reacted at a hydrogen flow of 15 L / hr and reactor temperatures of a) 175, b) 200, c) 225 and at d) 250 ° C and ambient pressure , The conversion of the educt (furfural) was mentioned temperatures a) to d) completely. The reaction effluents were condensed and as a result of the condensation, the reaction separated into two phases. The lower phase, about <1/5 of the total amount of the respective reaction effluent, was> 90% water and was discarded. Depending on the reaction temperature, the upper phase had the following compositions determined by gas chromatography:

Table 1

In addition to the organic portions, the upper phases of the discharges contained an additional 2 to 8% water.

The upper phase containing the reaction product 2-Me-THF was distilled in a packed column of length 1, 2 m, 2.5 cm inside diameter with 3x3 mm V2A metal rings as packing and the product 2-Me-THF could be obtained in> 99% purity.

Example 3

A copper catalyst with mineral support (composition in the unactivated state 25% CuO / 1% Cr ₂ O ₃ /74% SiO ₂ ) and a palladium-carbon catalyst (5% Pd on Supersorbon K, 4 mm strands) were prepared analogously to Example 2. installed in the reactor. At 225 ° C, the following composition of the reaction product was obtained:

85% 2-Me-THF, 5% 2-pentanone, <0.5% 3-pentanone, <0.5% 1-pentanol, 1% 2-pentanol, 4% THF, 0.5% furan, <0 , 5% methylfuran and other unidentified products.

Example 4

Analogously to Example 2 were 24.2 g of a copper catalyst with mineral support of the composition in the unactivated state 25% CuO / 1 ⁰ X) Cr ₂ Os / 74% SiO ₂ and 28.1 g of a platinum-carbon catalyst (5% Pt 4 mm strands Supersorbon K) installed in the reactor. At 225 ° C., the following composition of the reaction product was obtained: 82% 2-Me-THF, 4% 2-pentanone, 1% 3-pentanone, <0.5% 1-pentanol, 1% 2-pentanol, 3% THF, 0.5% furan, 1% methyl furan and other unidentified products.

Claims

claims

1. A process for the preparation of 2-methyltetrahydrofuran by one-stage hydrogenation of furfural with a hydrogen-containing gas in the presence of a structured bed of at least one copper catalyst and at least one catalyst containing at least one noble metal from groups 8, 9 and / or 10 of the Periodic Table having the elements applied to a carrier material.

2. A process for the preparation of 2-methyltetrahydrofuran by one-stage hydrogenation of furfural according to claim 1, characterized in that is hydrogenated in the presence of two catalysts in a structured bed.

3. The method according to claim 2, characterized in that the stream of the starting materials of the hydrogenation first flows through the copper catalyst (first catalyst) and then the noble metal-containing supported catalyst (second catalyst).

4. The method according to claim 2 or 3, characterized in that the structured bed of the two catalysts is located in one or more reactors.

5. The method according to any one of claims 1 to 4, characterized in that the first catalyst (copper catalyst) as active metals copper and one or more elements of groups 2, 6 and / or 12 of the Periodic Table of the

Has elements.

6. The method according to claim 2 to 5, characterized in that the first catalyst in addition to copper chromium, manganese, zinc and / or barium.

7. The method according to any one of claims 2 to 6, characterized in that the copper content of the first catalyst is at least 10 wt .-%.

8. The method according to any one of claims 2 to 7, characterized in that the second catalyst comprises palladium and / or platinum on a support.

9. The method according to claim 8, characterized in that the second catalyst comprises 0.1 to about 30 wt .-% palladium and / or platinum on a support.

10. The method according to claim 8 or 9, characterized in that the second catalyst comprises at least one element selected from Groups 1, 2, 4 and 7 to 12 of the Periodic Table of the Elements.

1 1. A method according to any one of claims 8 to 10, characterized in that activated carbon, alumina, silica, silicon carbide, calcium oxide, titanium dioxide and / or zirconia or mixtures thereof are used as a carrier of the second catalyst.

12. The method according to any one of claims 1 to 1 1, characterized in that the first catalyst forms 20 to 80% of the total height of the catalyst bed of the total height of the bed after the reactor head.

13. The method according to any one of claims 1 to 12, characterized in that the process is carried out in the liquid phase at a temperature of 150 to 250 C at 20 to 200 bar absolute.

14. The method according to claim 13, characterized in that the process is carried out in the presence or absence of a solvent.

15. The method according to any one of claims 1 to 12, characterized in that the process is carried out in the gas phase at a temperature of 150 to 250 C at 1 to 10 bar absolute.

16. The method according to any one of claims 1 to 15, characterized in that the process is carried out in recycle gas or circulation mode.